Resinous products or compositions including lacquers, paints, varnishes and other coating compositions



Patented May 15, 1934 UNITED STATES RESINOUS PRODUCTS OR COIHPOS ITIONSINCLUDING LACQUERS, PAINTS, VAR- NISHES AND OTHER COATING COMPOSI-Carleton Ellis, Montclair, N. J., assignor to Ellis-- Foster Company, acorporation of New.Jersey No Drawing. Original application October 10,

1925, Serial No. 61,839. Divided and this application May 28, 1930,Serial-No. 456,816

21 Claims.

This invention relates to resinous products or compositions includinglacquers, paints, varnishes and other coating compositions, and thelike, and relates especially to resinous products or compositionspreferably containing the products of reaction of glycerol, acrystalline organic acid, oily material comprising tung oil or the fattyacids thereof and a natural resin such as rosin.

As set forth in my application Serial No. 61,839 of which this is adivision glycerol in its various forms, dilute, concentrated, crude orrefined, or polyglycerol or glycerol ethers may be used; also otheranalogous polyhydric alcohols such as glycol, e. g., ethylene orpropylene glycol, diethylene glycol, and the like. Mixtures of thesepolyhydric alcohols or alcohol ethers likewise may be used in somecases. The crystalline organic acid includes such aliphatic acids astartaric, citric, malic, maleic, fumaric, mucic, succinic acids, and soforth; likewise aromatic acids such as phthalic, diphenic or otherpolybasic acids, or benzoic, salicylic or similar monobasic acids. Theanhydrides of these acids may be used to advantage in some cases.Phthalic anhydride in view of its low cost and the character of theresinous bodies produced may be used advantageously. Hence I may employnot only the acids themselves, but substances yieldingthese acids duringthe course of the reaction. Mixtures of crystalline acids also may beemployed. In this group of crystalline acids I prefer to employ those of10 or 12 car- I bons or less, these being mostly fairly watersoluble andcrystallizable, forming resins readily with glycerol which when solublein organic solvents are usually rather easily affected by Water. A verysubstantial degree of water-resistance is conferred by bringing into thereaction a siccative or drying oil of the nature of tung oil and theacid of a natural resin. Either pure tung oil it? self or the fattyacids thereof, or mixtures of these glycerides and the fatty acidthereof, may be used. It is sometimes opportune to use a glyceride oilwhich is somewhat acid, thereby securing cheaplyclude cyclic acids suchas naphthenic acids in some cases, used especially in conjunction withtung oil and/or its fatty acids. In general the oily componentconferring such water-resistance should preferably contain a siccativeconstituent, e. g., the fatty acids of a drying or semi-drying oil,specifically acids with two or more double bonds, that is, having ahigher degree of unsaturation than oleic acid. The latter acid, however,may be present. Tung oil therefore conforms excellently to thispreferred requirement. A specific and in some cases desirable form offatty oil or fatty acids is that prepared by blowing the oily material.In this way various drying or semi-drying oils may be blown and used inthe present composition. A blown tung oil may be used alone or it may bemixed with other blown oils, such as blown rapeseed oil. Mixtures ofblown and unblown oils likewise may be used. It has been noted in thespecification mentioned above that in the case of the blown oils theoxygen which is combined with the oil through the operation of blowingapparently serves as a locus of reaction to enable a deep-seatedresinification to take place. Among the oils which may be used inaddition to tung oil are linseed, fish, whale, rape, perilla, soya bean,sunflower, corn and cottonseed oils and their fatty acids. Any of theseor others of a similar character may be employed with the tung componentof the present invention. Tung oil has an especial degree ofwaterproofing power and hence is employed as a component of thepolyhydric alcohol resin to advantage. Tung oil and rosin are even morewater-resistant and the present invention proposes in part to avail ofthese substances to enhance the water-resistance of the resinousproduct. In Serial 61,839 the employment of resin acids such as those ofordinary rosin is proposed. These resin acids may be conveniently usedin the form of the natural resins themselves, such as ordinary rosin orcolophony or they may take a more purified form such as abietic acid. Inlike manner congo, pontianac and other natural resins of an acidcharacter may be utilized or mixtures of such natural resins of an acidcharacter. These natural resins, in general, have an acid number inexcess of 50.

In the present invention I preferably aim to produce soluble resins anddesire especially resins soluble in organic solvents used in the makingof lacquers or in the production of varnishes. 100

In the following examples the proportions given are parts by weight:

These resins may be prepared by heating the 11 several componentstogether to a temperature of 285-290 C. and maintaining .thistemperature for one-half hour to one hour or longer, according to thesize of the batch which is being prepared.

Prepared in proportions as given above the tung oil will be found tocombine at a temperature as lowas 200-210 C. This temperature ofcombination will, however, depend somewhat on the proportions of theother ingredients. It is understood thatwhere tung oil is specified thefatty acids of this oil may be used or a mixture of the oil and itsfatty acids.

Nitrocellulose solvents may be used to dissolve resins thus prepared andenable their incorporation with a cellulose compound such as nitrocellulose, especially low vicosity nitrocellulose.

Thus resins 1 and 4 may be incorporated with nitrocellulose to formclear lacquer by using resin Y 20 parts by weight, nitrocellulose 5parts, butyl acetate 30 parts, toluene 20- parts and ethyl alcohol 2parts.

In general I may follow the procedure set forth in Serial 61,839 for thepreparation of lacquer solutions with the aforesaid type of resin, usingnitrocellulose, especially low viscosity soluble cotton, employingvarious proportions, say equal parts, in a solvent mixture such asbenzol-anhydrous ethyl alcohol for the alcohol-solvent type ofnitrocellulose or butyl acetate-butanol for nitrocellulose notpossessing this particular form of solubility. Other solvents such asethyl carbonate, furfural, xylol, amyl acetate, acetone, methyl alcohol,and the like, may be employed according to requirements. Lacquercoatings of this character have shown a very great resistance onexposure tests.

The softer forms of the resins require no softeners or plasticizers, butwith the harder resins the employment of diethyl phthalate, diamylphthalate, tricresyl phosphate, acetin, castor oil and the like issometimes advantageous, when a very flexible nitrocellulose film isrequired.

Mixtures of any of the foregoing resins may be made for incorporationwith nitrocellulose and other synthetic or natural resins may be addedin appropriate and compatible proportion.

Pigments such as prussian blue or titanox should be ground with thevehicle in a ball or tube mill for a considerable period to attain avery fine suspension perhaps partly colloidal or dispersed.

Another phase of the present invention is that the resinificationreactions take place without the formation of insoluble productspreventing utilization in paints and varnishes. The product of thepresent invention is applicable in the making of oil varnishes ofparticular'durability.

For this purpose the resin, is incorporated by heatingwith a drying oilsuch as tung oil, linseed oil, and the like, a mixtureof parts tung oiland 10' parts linseed oil (proportions by weight) being desirable. Thus50 parts of resin as described in Examples 1 to 5 and 78 parts by weightof the linseed tung oil mixture as above were heated together at 320-330C.and allowed to body at this temperature for about 10 minutes. Then thetemperature was allowed to fall to about 200 C. and an equal weight ofthinner was added, this being a mixture of equal parts of turpentineand. heavy mineral spirits. Finally a liquid drier was introduced andthe resulting varnish allowed to settle to clarify or was illtered. Asmall amount of iron or other metallic substance present may react withphthalic acid or other acid material present to 1 91 1 9 .1-

pound which is insoluble and which although very slight in amount causesa turbidity that preferably, although not necessarily, should beremoved. Settling or filtration as noted accomplishes this.

In the particular oil varnishes represented by the foregoing the drierused was a mixture of lead and manganese compounds in the proportion of0.5 parts lead and 0.2 parts manganese,

based on the non-volatile components of the varnish.

Exterior exposure tests were carried on for a period of five months,using for the purpose panels carrying two coats of varnish. The panelsmade with varnishes prepared from resins Examples 1 to 5 inclusive didnot exhibit any failures during five months exposure. On the other hand,comparative tests with varnishes made from rosin ester, congo ester andoil soluble phenol formaldehyde resins showed marked indications ofdeterioration before the lapse of five months. The rosin ester varnishfailed five weeks prior to the time the five months test wasdiscontinued. The congo ester oil varnish showed results slightly betterthan the .rosin ester varnish. Panels coated with the oil varnishes madewith the aid of the phenol formaldehyde resins (these being gradesreadily obtainable in the market) were badly checked at the end of fivemonth. In addition to these comparative tests, panels also were exposedcarrying two coats of well known brands of spar varnish, one of whichwas known to have especially high content of siccative oil and thereforewas considered to be of unusual durability. At the end of the fivemonths exposure test these commercial spar varnishes were in bettercondition than the ester gum and phenol formaldehyde varnishes, but thesurface of both of these spar varnishes were somewhat checked and theywere not in the perfect condition of the tung rosin phthalic glyceridecompositions of the present invention.

Both lacquers and oil varnishes with or without fillers and/or pigmentsmay be heat-dried or baked after applying to a suitable surface in noorder to obtain harder and more resistant coatings, and also may bebaked in shaped masses for the purpose of forming insulating material orotherwise in the field of plastic molding.

As will be evident from the foregoing, the proportions of the reactingingredients may be varied according to required conditions. Likewise theorder of mixing may be varied ii desired. Preferably I heat all theingredients forming the resin, together, asa one stage procedure as thisconstitutes a more simple operation than successive additions of theseveral components. However, in some casesImay form a resin nucleus fromtwo or more of the resinii'ying constituents and add thereto graduallyor otherwise the remaining ingredients.

What I claim is:

1. A resinous product comprising a glycerol mixed ester of tung oilacids, phthalic anhydride and rosin.

2. A resinous product comprising a glycerol mixed ester of tung oilacids, phthalic anhydride and natural resin acid.

3. A resinous'product comprising a polyhydric alcohol mixed ester oftung oil acid, natural resin acid and polybasic organic acid.

alcohol mixed ester of tung oil acid, linseed oil 5. The process ofproducing a synthetic resin which comprises heating to reactiontemperature a react-ion mass containing a polyhydric alcohol, apolybasic acid, a drying oil acid and a natural resin. I

6. The process of producing a synthetic resin which comprises heating toreaction temperature a reaction mass containing a polyhydric alcohol, apolybasic acid, a drying oil acid, a natural resin and a drying oil.

7. The process of producing a synthetic resin which comprises heating toreaction temperature a reaction mass containing glycerol, phthalic acid,linseed oil and rosin.

8. The process of claim 5 in which the natural resin has an acid numberof at least 50.

9. A new composition of matter comprising a mixed ester in which thealcohol radical is that of a polyhydric alcohol and the acid radicalsare those of a polybasic acid, a drying oil acid and a natural resinacid.

10. A coating composition comprising a mixed ester and a solventtherefor, said mixed ester having as the alcohol component a polyhydricalcohol and as the acid components a polybasic acid, a natural resinacid and acids obtainable by the hydrolysis of drying oil.

11. A coating composition comprising a mixed ester of glycerin and asolvent therefor, said mixed ester having as the acid componentsphthalic acid, a. natural resin acid and acids obtainable by thehydrolysis of drying oil.

12. Sheet metal carrying a tightly adhering coating comprising a mixedester of glycerin having as the acid components phthalic acid, a

natural resin acid and acids obtainable by the hydrolysis of drying oil.

13. The process of producing a synthetic resin which comprises heatingto reaction temperature a reaction mass containing glycerol, phthalicacid, linseed oil acid and rosin.

14. The process of producing a substantially homogeneousdrying-oil-modifled polyhydric alcohol-polybasic acid resin whichcomprises heating to reaction temperature amass containing the radicalsof a polyhydric alcohol and a polybasic acid, with a drying oil androsin.

, 15.A resinous product which on saponification yields a polyhydricalcohol, a polybasic acid, a drying oil acid and rosin acids.

16. A resinous product which on saponification yields glycerol, phthalicacid, linseed oil acids, and rosin acids. a

17. A resinous product which on sapom'fication yields glycerol, phthalicacid, tung oil acids and .rosin acids.

